Process for imparting rot and wrinkle resistant finish to a cellulosic textile material and the resulting textile



United States Patent 3,323,939 PROCESS FOR IMPARTING ROT AND WRINKLERESISTANT FINISH TO A CELLULOSIC TEX- ;EE MATERIAL AND THE RESULTINGTEX- William Julius Van Loo, Jr., Middlesex, N.J., assignor to AmericanCyanamid Company, Stamford, Conn., a corporation of Maine No Drawing.Filed Mar. 9, 1964, Ser. No. 350,533 13 Claims. (Cl. 117-76) The presentinvention relates to processes for imp-roving the wrinkle resistantproperties of textile materials and to the textile materials sofinished. More particularly the invention relates to processes fortreating textile materials whereby they are made both crease resistantand rot resistant.

The primary object of the invention is accomplished by treatingcellulosic textile materials, which have previously been treated for rotresistance by a wet steam process, with a non-aqueous solution of adifunctional compound and heat curing the thus treated material. Thisfinishing treatment imparts both a crease resistance and a rotresistance to the textile material without seriously affecting thetensile strength of the material.

It is known that cellulosic textile materials can be treated withhardenable aminoplasts to render the materials resistant to the attackof microorganisms. However, while a degree of rot resistance is obtainedfrom these resins, it is accomplished by a loss in the tensile strengthof the materials. In US. Patent No. 2,763,574 there is described a wetsteam process for treating materials with these hardenable aminoplastswhereby rot resistance is imparted to the textiles without loss offabric strength. This wet steam process will be more fully described ina later paragraph. While this type of treatment, as described in theabove-identified patent, imparts rot resistance to the textiles, it doesnot impart any other improvements in the major physical propertiesdesired in fabrics such as wrinkle resistance or wrinkle recovery.

It is also known that cellulose-containing textile material can betreated with creaseproofing resins to impart wrinkle recovery propertiesto the material. These creaseproofing resins are generally applied tofabrics free from sizes or other finishes, and while they improve thewrinkle recovery properties of the fabric, there is always suffered aloss in tensile strength. Such creaseproofing resins, like those of thehardenable aminoplasts, are applied to the materials in a water-solublestate and then dried and cured. However, while a fabric which has beenfinished with these resins is characterized by improved wrinkleresistance, the effect of the curing of the resin whereby cross-linkingof the fibers is effected results in reducing the tensile strength ofthe material.

The inventor has found that by treating the textile materials with -aresin capable of imparting rot resistance to the material by the wetsteam process and then subsequently treating it with a difunctionalcompound from a non-aqueous solution and heat curing the same, thatcreaseproofing properties are imparted to the textile without the use ofa creaseproofing resin.

When creaseproofing resins are normally applied to textiles from aqueoussolutions, the fibers swell so that the resin can cross-link and reactwith the fibers during curing, thereby giving it crease resistance.However, the difunctional compounds used in this invention are waterinsoluble or water reactive and thus are not applicable from an aqueoussolution. It will be appreciated that the application of thedifnnctional compound from nonaqueous solutions will not produce fiberswelling, and without fiber swelling the compounds normally would not beexpected to impart any wrinkle recovery properties to 3,323,939 PatentedJune 6, 1967 ice the materials. In addition, if the materials weretreated with these compounds from non-aqueous solutions there would beexcessive discoloration and loss in tensile strength of the materials.

However, the inventor has found that if these same non-aqueous solutionsof the difunctional compounds are applied to a cellulosic material whichhas previously been treated for rot resistance by the wet steam processan unexpected result is obtained. It is found that crease resistantproperties are imparted to the material without any substantial loss inthe rot resistant properties given to the material by the resintreatment or in the tensile strength of the material.

The wet steam process as described in US. Patent No. 2,763,574 isessentially a process wherein the hardenable aminoplast is cured on thefabric in the presence of about 45% of the water in the originalimpregnating aqueous resin solution. By' fixing the aminoplast withlittle or no drying of the impregnated fibrous material, tensilestrength properties are retained. The inventor pretreats the cellulosictextile materials with hardenable aminoplasts by this wet steam process.This process used by the inventor involves applying to the fabric by anyconvenient method an aqueous solution of the aminoplast resin containinga curing catalyst. The fabric is then rolled up tightly on a dowel, rodor shell and placed in a suitable container of a size such that verylittle free space exists. The container is closed but is fitted with asmall opening to allow for the release of potential pressure build-upbut insufiiciently large to allow for the significant escape ofmoisture. In the examples which follow, the complete assembly was thenplaced in an oven at 210 F. and allowed to remain for 2.5 hours. Theassembly is then removed and the fabric unrolled and allowed to dry atroom temperature. As can be seen from the reference patent, there areother ways of elfecting affixation of the aminoplast in the presence ofmoisture without substantial drying and these are well within the scopeof this invention.

Suitable hardenable aminoplasts which can be used to pretreat the fabricby the wet steam process include condensations of formaldehyde withcompounds such as urea, thiourea, cyanamide, dicyandiamide, biguanide,melamine, formoguanamine, acetoguauamine and so forth, including theiralkyl and acyl compounds. Particularly suitable are the water-solublecondensation products of melamine and formaldehyde and in particular themethylol or methoxymethyl derivatives of melamine. These include variouscompounds as methylated methylol melamines, such ashexa(methoxymethyl)melamine and the preferred dimethylol melamine.

Advantageously, curing catalysts are added to the solutions of theresins, and suitable catalysts include diacetin, monochlorohydrin,dichlorohydrin, glycol ethyl etheracetate, glycol methyl ether acetateand the like, with the preferred catalyst being diacetin.

These resins are applied in their aqueous solutions by the wet steamprocess as previously described through general methods of applicationsuch as spraying, dipping, immersion or padding. Generally the resinsare applied in an amount of from 1 to 30% resin solids based on theweight of the fabric and generally included is a curing catalystamounting from 2 to 25% based on the weight of the resin. When properlyprocessed, the treated textile material will show approximately orhigher of the initial amount of resin applied remaining after boilingfor 30 minutes in water. The amount of resin fixation is determined bynitrogen analysis.

The cellulosic textile materials which can be used include cotton,rayon, linen, hemp, jute or the like. They may be present in combinationwith up to 50% of other natural or synthetic fibers 'such as wool,acetate, nylon, polyester fibers such as Dacron, acrylic fibers such asCreslan, Orlon, Acrilan and the like. Preferably, the textile materialis a formed woven cotton fabric.

The difunctional compounds used in the second step of this two-stepprocess refers to those types of compounds having two functional orreactive groups attached to a divalent radical. These compounds may beused in combination with a suitable catalyst. Examples of difunctionalcompounds contemplated in this invention include those represented bythe following general formula:

whereinX can represent hydrogen or halogen and R can be (CH with n aninteger from zero to 12, arylene or lower alkylarylene. This formulaincludes such specific compounds as oxalyl chloride, succinyl chloride,glutaryl chloride, pimelyl chloride, succinaldehyde, pimelaldehyde,terephthaloyl chloride, terephthalaldehyde, S-methylisophthaloylchloride and S-methylisophthalaldehyde.

Other suitable difunctional compounds include compounds which containtwo functional or reactive halomethyl groups and in particularchloromethyl groups per molecule. The divalent radical to which thesereactive groups may be attached includes oxygen and residues of loweralkylene ethers, lower dialkylene polyethers, alkylenediamine andsubstituted alkylenediamines, alkyl'enediamides. and substitutedalkylenediamides, urea, imidazolidones, pyrimidinones, uron, triazones,triaminotriazines, diaminodiazines, and diurein. Examples of thesechloromethyl ethers include such compounds as chloromethyl ether,1,2-ethylene bis(chloromethyl ether), bis(chloromethyl ether) ofdiethylene glycol, 1,2-propylene bis(chloromethyl ether),N,N'-di(chloromethyl)propylene-l,3- diamine,N,N-di(chloromethyl)succinamide, N,N-di (chloromethyl)urea, N,N'di(chloromethyl)imidazolidone-2, N,N-di(chloromethyl)pyrimidinOne-Z,N,N'-di (chloromethyl)uron, N N -di(chloromethyl) N-(betahydroxyethyl)tetrahydrotriazone-Z, N,N'-di(chloromethyl)melamine,N,N'-di(chloromethyl)acetoguanamine or N,N',N,N"'-tetra (chloromethyl)acetylenediurein.

Also suitable for this invention are compounds which contain twoaziridinyl groups per molecule. Such compounds are characterized by thefollowing formula:

R20 X C l\ 320 i \CRH wherein R may be hydrogen or lower alkyl and X maybe oxygen or sulfur and Ycan be another aziridinyl group, a. lower alkylsubstituted aziridinyl group, aryl or lower alkylether. Examples ofthese include such compounds as tris(aziridinyl)phosphine oxide,tris(aziridinyl)phosphine sulfide, tris(Z-methylaziridinyl)phosphineoxide, phenylbis(2-methylaziridinyl)phosphine oxide, or ethoxy-bis(2-methylaziridinyl)phosphine oxide. 4

Certain compounds which are water insoluble and contain at least tworeactive alkylol or alkoxyalkyl groups are also suitable for thisinvention. These compounds include the methylol or alkoxymethylderivatives of alkylene diamides of more than six carbon atoms. Forexample, N,N'-dimethylolazelaamide. Also suitable are the ethoxymethylor higher alkoxymethyl derivatives of urea and uron. For example, N,N'bis(n-propoxymethyl)urea and N,N'-bis(n-propoxymethyl)uron. In addition,the water insoluble higher alkoxymethyl derivatives of triaminotriazines are suitable difunctional agents. This includes among othercompounds N,N',N"-tris(n-butoxymethyl) N,N-dimethylol melamine.

The catalysts which may be advantageously used with these heat curabledifunctional compounds may be metal salts such as the chlorides andnitrates of magnesium, zinc and aluminum. Amine and alkanolamine saltssuch 4. as ethanolamine hydrochloride may also be employed as catalysts.I V v I Since these difunctional compounds are water insoluble or waterreactive, they can only be applied from nonaqueous solvent solutions.Suitable solvents which can be used and which are compatible with thecatalysts used, if any, include such solvents as acetone, methyl ethylketone, benzene, toluene and the like.

These difunctional compounds which are applied .in the form ofnon-aqueous solution are usually applied in an amount of from 1 to 30%based on the weight of the fabric. The catalyst used, if any, is usuallyfrom about .5% to about 40% based onthe compound solids.

After the material is treated with these difunctional compounds, it isusually dried at about 150 to 400 F.

for anywhere from .25 to 3.0 minutes. It is then cured at about 250 to500 F. for anywhere from .5 to 3.0 minutes. Since, in general, time andtemperature are inversely proportional, i.e., as the time increases, thetemperature may be lowered and as the time decreases, the temperaturemay be elevated, wide limits of time and temperature can be employed.

The non-aqueous solution of the difunctional compound may be applied byany convenient means such as spraying, dipping, immersion or padding.The preferred method is by padding through a microset padder.

By combining this wet steam process for applying a. rot resistant orpre-treatment resin to a textile with a subsequent treatment of anon-aqueous solution of a difunctional compound and heat curing thesame, new and unexpected results are obtained. The subsequent exampleswill show that if these cellulosic materials are treated merely with ahardenable aminoplast resin by the wet steam process as described in US.Patent No. 2,763,574, the materials have rot resistance and no loss intensile strength, but no wrinkle recovery. However, the results alsoshow that if these materials which have been pretreated by the wetsteam-process are subsequently treated with a difunctional compound,they show good wrinkleresistance without substantial loss in the tensilestrength or the rot resistance properties previously obtained. Thisimprovement in the wrinkle resistant properties of the textile materialsis accomplished by the applicationof these difunctional compounds whichby themselves would give to the textile materials no wrinkle resistantproperties. Thus the inventor has found that the wrinkle resistantproperties of textiles may be greatly enhanced without a substantialloss of tensile strength by treating them with two separate treatmentswhich by themselves would not impart to the textiles any wrinkleresistant properties. Because of this treatment there is obtained acombined rot resistant and wrinkle resistant finish for cellulosictextile material.

The following examples illustrate the invention.

Example 1 Cotton percale x 80) was treated with 10% solids of dimethylolmelamine containing 10% diacetin (on weight of resin) as a catalyst bythe wet steam process previously described. The wet fixation time was2.5 hours and the percent resin fixation was determined by nitrogenanalysis. Initially the treated fabric had a nitrogen content of 3.95%and after boiling for 30 minutes in water, it was 2.1 1% indicating that54% of the resin was fixed to the fabric.

The nitrogen content indicates that sufiicient resin has been afiixed tothe cotton material to assure rot resistance as at least 2% nitrogen isall that is necessary to obtain a rot resistant cellulosic material.

The wrinkle recovery of the fabric was measured on a Monsanto WrinkleRecovery Tester and the'values are reported in degrees, following thetentative test method of 66-1956 described on page 158 of the 1957Technical Manual and Year Book of the American Association of TextileChemists and Colorists, vol. 33.

The tensile strength was measured on a Scott Tester according to ASTMstandards.

The results of the tests run on the fabrics indicated that untreatedcotton fabric had a wrinkle recovery of 168 degrees and a tensilestrength of 91 pounds. The cotton fabric which had been treated withdimethylol melamine by the wet steam process had a wrinkle recovery of171 degrees and a tensile strength of 91 pounds. While the fabric hasrot resistance, the treatment has given the fabric no wrinkle resistanceand has not adversely affected its tensile strength.

Example 2 A sample of a fabric wet steam treated as in Example 1 wassubsequently treated with 5% solids based on the weight of the fabric ofsuccinyl chloride from an acetone solution through a microset padder.The thus treated material was dried for 2 minutes at 225 F. and curedfor 1.5 minutes at 350 F. in a circulating hot air oven. The fabric wasthen tested for wrinkle recovery and tensile strength by the testmethods outlined in Example 1. Results indicated that the fabric now hada wrinkle recovery of 238 degrees with a tensile strength of 62 pounds.

While an application of succinyl chloride alone to the material wouldhave destroyed it and given it no wrinkle recovery, the results indicatethat when used in combination with the wet steam pretreatment, goodwrinkle recovery properties are obtained over those which had beenmerely pretreated as shown in Example 1. The results also show that thetensile strength of the material is not affected too adversely. Whenother acid chlorides such as oxalyl chloride, glutaryl chloride orpimelyl chloride are substituted for the succinyl chloride or in mixturewith it, good wrinkle recovery properties are also obtained.

Example 3 A sample of the fabric wet steam treated as in Example 1 wastreated with an aqueous solution of .7% based on the weight of thefabric of magnesium chloride as a suitable catalyst for the difunctionalcompound through a microset padder. The thus treated fabric was driedfor 2 minutes at 225 F. in a circulating hot air oven. The fabric wasthen treated with a 5% solution of terephthalaldehyde in acetone througha microset padder. After obtaining a wet pickup of 100%, the fabric wasdried for 2 minutes at 225 F. and cured for 1.5 minutes at 350 F. in acirculating hot air oven.

The fabric was then tested for its wrinkle recovery and tensile strengthby the test methods of Example 1. The results indicated that the fabricnow had a wrinkle recovery of 246 degrees with a tensile strength of 68pounds. The results here indicate that when terephthalaldehyde is usedin combination with an aminoplast resin which has been applied by thewet steam process, that good wrinkle recovery properties are obtained.

When other aldehydes such as succinaldehyde, pimealdehyde,S-methylisophthalaldehyde are substituted for the terephthalaldehyde orin mixture with it, good wrinkle recovery properties are also obtained.

Example 4 A sample of the fabric treated by the wet steam process asdescribed in Example 1 was treated with 5% solids based on the weight ofthe fabric of terephthaloyl chloride in an acetone solution through amicroset padder. The thus treated fabric was dried for 2 minutes at 225F. in a circulating hot air oven, and cured for 1.5 minutes at 350 F.

The fabric was then tested for its wrinkle recovery and tensile strengthby the test methods of Example 1. The results indicated that the fabrichad a wrinkle recovery of 238 degrees and a tensile strength of 64pounds. These results indicate that when terephthaloyl chloride is usedin combination with the rot resistant aminoplast resin applied by thewet steam process, that the material has obtained good wrinkle recoveryproperties without a great loss in tensile strength.

When S-methylisophthaloyl chloride was substituted for terephthaloylchloride or in mixture with it, good wrinkle recovery properties werealso obtained.

It will be appreciated that at any stage in the abovedescribed processother textile finishing agents and auxiliaries may be employed, such assofteners, lubricants, brighteners, odors, and the like.

I claim:

7 1. A process for imparting to cellulose containing textile materialsrot and wrinkle resistance with minimum tensile strength losses, whichcomprises treating the material with an aqueous impregnating solution ofa melamine formaldehyde resin in an amount of from 1 to about 30% basedon the weight of the material which contains a curing catalyst, curingsaid resin impregnated material in the presence of water, subsequentlyapplying to said treated material a non-aqueous solution of a member ofthe group consisting of water insoluble and water reactive difunctionalcompounds in an amount from 1 to about 30% based on the Weight of thematerial of said difunctional compounds and heat curing the thus treatedmaterial.

2. A process for importing to cellulose containing textile materials rotand wrinkle resistance with minimum tensile strength losses, whichcomprises treating the material with an aqueous impregnating solution ofa melamine formaldehyde resin containing a curing catalyst so as toapply from 1 to 30% of said resin based on the weight of the material,curing said resin impregnated material in the presence of water,subsequently applying to said material a non-aqueous solution of from 1to 30% based on the weight of the material of a difunctional compound ofthe following formula:

where X is a member of the group consisting of halogen and hydrogen andR is a member of the group consisting of (CH with n an integer from zeroto 12, arylene or lower alkylarylene and heat curing the thus treatedmaterial.

3. A process according to claim 2 wherein the melamine formaldehyderesin is applied in an amount of from 1 to about 30% based on the weightof the material and the difunctional compound is applied in an amount offrom 1 to 30% based on the weight of the material.

4. A process according to claim 3 wherein the difunctional compound issuccinylchloride.

5. A process according to claim 3 wherein the difunctional compound isterephthalaldehyde.

6. A process according to claim 3 wherein the difunctional compound isterephthaloyl chloride.

7. A process for imparting to cellulose containing textile materials rotand wrinkle resistance with minimum tensile strength losses, whichcomprises treating the material with an aqueous impregnating solution ofdimethylol melamine with a curing catalyst so as to apply from 1 to 30%of said dimethylol melamine to said materials curing said resinimpregnated material in the presence of water, subsequently applying tosaid material a non-aqueous solution of succinyl chloride so as to applyfrom 1 to 30% of said chloride to the material and heat curing the thustreated material.

8. A rot and wrinkle resistant cellulose containing textile materialhaving thereon from 1 to 30% based on the weight of the material of awet cured melamine formaldehyde resin and from 1 to 30% based on theweight of the material of a dry cured member of the group consisting ofwater insoluble and water reactive difunctional compounds.

9. A rot and wrinkle resistant cellulose containing textile materialhaving thereon from 1 to 30% based on the the following formula:

X-CRCX wherein X is a member of the group consisting of halogen .andhydrogen and R is a member of the group consisting of (CH with m aninteger from Zero to 12, arylene or lower alkylarylene. v

10. A textile material according to claim 9 wherein the difunctionalcompound is'succinyl chloride.

11. A textile material according to claim 9 wherein the difunctionalcompound is terephthaloyl chloride.

12. A textile material according to claim 9 wherein the difunctionalcompound is terephthalaldehyde.

13. A rot and wrinkle resistant cellulose containing textile materialhaving thereon a'dimethylolmalamine resin cured in the presence of Waterand a dry cured nonaqueous solution of. succinyl chloride.

References Cited UNITED STATES PATENTS 'WILLIAM D. MARTIN, PrimaryExaminer;

T. G. DAVIS, Assistant Examiner.

Dedication 3,323,939. -Mlliam Julius Van Loo, Jr.. Middlesex, NJ.PROCESS FOR IMPARTING ROT AND WRINKLE RESISTANT FINISH TO A CELLULOSICTEXTILE MATERIAL AND THE RESULTING TEXTILE. Patent dated June 6, 1967.Dedication filed Mar. 4, 1983, by the asaignee, American Cyanamid Co.

Hereby dedicates the remaining term of said patent to the Public.

[Oflicial Gazette May 31, 1983.]

1. A PROCESS FOR IMPARTING TO CELLULOSE CONTAINING TEXTILE MATERIALS ROTAND WRINKLE RESISTANCE WITH MINIMUM TENSILE STRENGTH LOSES, WHICHCOMPRISES TREATING THE MATERIAL WITH AN AQUEOUS IMPREGNATING SOLUTION OFA MELAMINE FORMALDEHYDE RESIN IN AN AMOUNT OF FROM 1 TO ABOUT 30% BASEDON THE WEIGHT OF THE MATERIAL WHICH CONTAINS A CURING CATALYST, CURINGSAID RESIN IMPREGNATED MATERIAL IN THE PRESENCE OF WATER, SUBSEQUENTLYAPPLYING TO SAID TREATED MATERIAL A NON-AQUEOUS SOLUTION OF A MEMBER OFTHE GROUP CONSISTING OF WATER INSOLUBLE AND WATER REACTIVE DIFUNCTIONALCOMPOUNDS IN AN AMOUNT FROM 1 TO ABOUT 30% BASED ON THE WEIGHT OF THEMATERIAL OF SAID DIFUNCTIONAL COMPOUNDS AND HEAT CURING THE THUS TREATEDMATERIAL.